(Meth)acrylate-based compositions

ABSTRACT

A novel methacrylate-based composition is disclosed. The composition is preferably used as an adhesive. The composition comprises an acrylate-based or methacrylate-based ester monomer, a catalyst, a chlorinated or chlorosulfonated polyethylene polymer resin and a graft co-polymer resin. The chlorinated polyethylene polymer resin used includes organic sulfonyl chloride. The composition preferably further includes an acrylate-based or methacrylate-based acid monomer, and a catalyst activator. A preferred chlorosulfonated polyethylene polymer resin contains about 43 weight percent chlorine, about 1.1 weight percent sulfur, and about 34 millimoles sulfonyl chloride moiety per 100 grams thereof. Preferred graft co-polymer resins are ABS, MBS, MABS, ASA, all-acrylic, SA EPDM and MAS. More-preferred graft co-polymer resins are MABS, ASA, all-acrylic and MBS. Most-preferred graft co-polymer resins are MABS and ASA. A preferred methacrylate-based acid monomer is methacrylic acid. Preferred methacrylate-based ester monomers are methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and tetrahydrofurfuryl methacrylate. More-preferred methacrylate-based ester monomers are methyl methacrylate and ethyl methacrylate. A most-preferred methacrylate-based ester monomer is methyl methacrylate. The composition possesses enhanced compression shear strength, lap shear strength, peel strength and impact strength adhesive physical properties.

BACKGROUND OF THE INVENTION

This invention is directed to novel acrylate-based or methacrylate-based compositions which are preferably used as adhesives. More particularly, this invention is directed to novel methacrylate-based compositions which include relative effective amounts of chlorosulfonated polyethylene and graft polymers for substantially enhancing overall adhesive properties of the compositions.

A variety of patents (for example, U.S. Pat. Nos. 3,890,407 and 4,112,013 to Briggs, Jr. et al, U.S. Pat. No. 4,118,436 to Craven, U.S. Pat. No. 4,126,504 to Wolinski et al, U.S. Pat. No. 4,127,699 to Aumiller et al, U.S. Pat. No. 4,182,644 to Briggs, Jr. et al, U.S. Pat. No. 4,223,115 to Zalucha et al, U.S. Pat. No. 4,226,954 to Pelosi, U.S. Pat. No. 4,263,419 to Piestert et al, and U.S. Pat. No. 4,293,665 to Zalucha et al) teach generally that acrylate-based or methacrylate-based adhesives can be obtained from mixtures which include effective amounts of chlorosulfonated polyethylene. Briefly put, of the above-mentioned patents which disclose adhesive compositions, adhesive physical properties of such compositions are described either in terms of lap shear strength, or T-peel strength, or both. Some of these patents, moreover, specifically teach that other adhesive properties or preparative features of the therein disclosed compositions can otherwise become enhanced (for example, substantially no premixing of composition ingredients being necessary prior to use thereof; or relatively fast setting of the composition, and strong durable bonds being formed; or adhesion to oily metal surfaces) through inclusion of chlorosulfonated polyethylene therein.

As the following terms are used throughout this application, acrylate-based adhesives are based upon the chemical structure: ##STR1## and methacrylate-based adhesives are based upon the chemical structure: ##STR2## When R is hydrogen, for example, the acrylate-based and methacrylate-based adhesives are based upon acrylic acid and methacrylic acid respectively; or, when R is a methyl group, the acrylate-based and methacrylate-based adhesives are based upon methyl acrylate and methyl methacrylate respectively.

Graft Co-polymers

Polymers comprising relatively long sequences or chains of at least two different monomers or monomeric units can have such chains linked together in a "block" or "graft" arrangement. A block arrangement is linear and is formed from at least two alternating monomeric units. The block arrangement, moreover, can further be formed from monomeric unit sequences which alternate (or repeat) in either an ordered or a random fashion. See U.S. Pat. No. 4.332,858 to Saitoh et al. Block or graft polymers are often referred to as co-polymers, terpolymers or multi-component polymers.

In the graft arrangement, one or more of such sequences are grafted onto a backbone of yet another sequence, such grafting usually taking place at each one of a plurality of grafting sites of the backbone. See, for example, Textbook of Polymer Science, 2nd Edition, by F. W. Billmeyer, Jr., published by Wiley-Interscience, a Division of John Wiley and Sons, Inc. (1971), at pp. 350-351. In the graft co-polymer art, when the backbone is a rubber or a rubber-like material and the grafted sequences are vinyl or acrylate- or methacrylate-based monomers, the backbones are often referred to as the "core" of the graft co-polymer. Sequences grafted onto the core form a "shell" theresurrounding.

Such graft co-polymers, frequently referred to as resins, often take the form of a plurality of relatively small particles, especially when the rubber or rubber-like material or the grafted portions or both of these are crosslinked. Not all graft co-polymer resins have such a core-and-shell configuration (or morphology), however. Some, for example, may have a more continuous (i.e., homogeneous) microstructure which, quite often, takes the form of interpenetrating (yet distinct) polymer networks.

Graft co-polymer resins which have the core-and-shell configuration are currently primarily used as modifiers in certain polymer systems. For example, certain ABS (acrylonitrile-butadiene-styrene) or MBS (methacrylate-butadiene-styrene) resins, when added to PVC (polyvinyl chloride), are well-known impact-resistance or processability modifiers.

Graft co-polymers, per se, are generally not added to adhesive compositions to augment or enhance the adhesive qualities thereof. For example, although U.S. Pat. No. 3,870,675 to Kusayama et al teaches (at column 2, lines 6-27) that an acrylate-based or methacrylate-based adhesive composition can include an ABS resin, the ABS resin therein is included primarily because of its rubber-like characteristics. Certain types of ABS resin, moreover, are well known rubber-like materials and, accordingly, are often used interchangeably with other rubber-like materials. Such types of ABS resin, furthermore, are known to be two-phase systems comprising inclusions of a rubber or a rubber-like phase in a continuous, glassy phase, wherein the continuous phase forms a matrix for the two-phase system. It is further well known that obtaining preferred rubber-like qualities, as to such types of ABS resin, requires selectively grafting, as between the continuous and rubber or rubber-like phases thereof. See, for example, Textbook of Polymer Science, cited above, at page 408. The '675 patent, accordingly, further mentions other compositions wherein other rubber or rubber-like materials have been substituted for ABS. (In the '675 patent, see column 2, lines 15-19 in connection with column 3, lines 42-45 and column 6, Table 3.) The adhesive compositions of the '675 patent have adhesive properties (such as, for example, tensile strength after contact, shear strength and impact strength) which render the '675 adhesives substantially different (e.g., as to application or use) from the chlorosulfonated polyethylene-based compositions mentioned above.

Yet another patent, U.S. Pat. No. 4,287,106 to Forgo et al, discloses an acrylate-based or methacrylate-based adhesive composition including ABS polymers (see column 2, lines 33-48), but specifically teaches away from inclusion therein of chlorosulfonated polyethylene (column 1, lines 14-34 in connection with: column 1, lines 57-68; column 2, lines 1-32; column 8, lines 41-56; and column 9, lines 50-64). More specifically, the '106 patent teaches that a chlorosulfonated amide or imide, instead of chlorosulfonated polyethylene, produces an adhesive composition having certain desirable adhesive qualities or properties.

Up until the present time, moreover, it was thought that addition of rubber or rubber-like polymers, such as ABS, to acrylate-based or methacrylate-based adhesive compositions would enhance a first class (or group) of adhesive properties of the compositions, but that further addition (or inclusion) of an additional ingredient (or component) such as, for example, a chlorosulfonated polyethylene (so as to enhance a second class or group of adhesive properties of the composition) would probably render relatively less effective the first group of adhesive properties or would otherwise undesirably affect the overall adhesive performance of the composition. The '106 patent to Forgo, discussed above, accordingly, specifically teaches away from such a combined inclusion of ABS polymers and chlorosulfonated polyethylene in an acrylate-based or methacrylate-based adhesive composition.

OBJECTS AND SUMMARY OF THE INVENTION

It is therefore a general object of this invention to provide a novel methacrylate-based adhesive composition.

A more specific object is to provide such an adhesive composition which includes relative effective amounts of chlorosulfonated polyethylene resin and a graft co-polymer for substantially enhancing overall adhesive qualities or properties of the composition.

A yet more specific object is to provide such a composition having relatively high compression shear strength (i.e., provides relatively strong adhesive bonds as between most plastic materials), lap shear strength (i.e., provides relatively strong adhesive bonds as between most metallic materials), peel strength and impact strength, which, in turn, can generally be understood to mean that such composition possesses substantially enhanced overall adhesive qualities or properties.

A related object is to provide methods of bonding surfaces together using the adhesive composition of the present invention.

Briefly, and in accordance with the foregoing objects, a novel methacrylate-based adhesive composition, according to the present invention, comprises an acrylate-based or methacrylate-based ester monomer, a catalyst and relative effective amounts of a chlorinated or chlorosulfonated polyethylene polymer resin and a graft co-polymer resin for substantially enhancing overall adhesive qualities or properties of the composition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The composition of the present invention can comprise an acrylate-based ester monomer. Preferably, however, the composition comprises a methacrylate-based ester monomer. Such a methacrylate-based ester monomer is preferably selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and tetrahydrofurfuryl methacrylate. Still more preferably, the methacrylate-based ester monomer is selected from the group consisting of methyl methacrylate and ethyl methacrylate. Most preferably, the methacrylate-based ester monomer is methyl methacrylate.

In certain instances it is desirable that the methacrylate-based ester monomer include an effective amount of an inhibitor for inhibiting or otherwise preventing polymerization of the ester monomer. For example, below-presented examples of the composition ot the present invention, which therein included methyl methacrylate ester monomer, generally contained from about 50 to about 90 parts per million (ppm) of hydroquinone in the ester monomer as such an inhibitor. Throughout this application the term ppm is based on total weight of the named material. In this sense, the term translates into inclusion of from about 50 to about 90 pounds of hydroquinone per million pounds of ester monomer, the monomer weight being based upon methyl methacrylate and including the hydroquinone.

The composition can further include an acrylate-based acid monomer such as acrylic acid. Inclusion of an acid monomer, however, is entirely optional. In certain instances it may be desirable to exclude use of the acid monomer. See, for example, below-presented discussion which is directed to explanation of example VI. Preferably, however, the composition further includes methacrylic acid. Such methacrylic acid, moreover, in below-presented examples (of the compositions of the present invention), generally contained, for reasons discussed immediately above, about 250 ppm of hydroquinone in the acid monomer as an inhibitor.

The composition further includes a catalyst. For purposes of the present invention, the term "catalyst" means a free-radical generator. As discussed in my above-cited U.S. Pat. No. 4,112,013 at column 2, lines 23-24 thereof, such a free-radical generator can be an organic peroxide, an organic hydroperoxide, a perester, or a peracid. As is well known in the field of acrylate-based and methacrylate-based compositions, such a catalyst is used for triggering polymerization of acrylate-based and methacrylate-based monomers. A preferred catalyst, appearing in below-presented examples of the compositions of the present invention, is cumene hydroperoxide, a free-radical generating organic hydroperoxide.

The composition additionally includes either chlorinated or chlorosulfonated polyethylene polymer resin. I have found, on previous occasion (see, for example, my U.S. Pat. No. 3,890,407), that chlorinated polyethylene can be substituted for chlorosulfonated polyethylene. When chlorinated polyethylene is substituted, however, organic sulfonyl chloride is preferably further included.

Preferably, however, the composition of the instant invention includes chlorosulfonated polyethylene polymer, the resin which, in turn, preferably contains from about 25 to about 70 weight percent chlorine and from about 3 to about 160 millimoles of sulfonyl chloride moiety per 100 grams thereof. Such polymer resin is described more fully in my above-cited patents (i.e., U.S. Pat. Nos. 3,890,407, 4,112,013 and 4,182,644) which I now incorporate by reference. Briefly paraphrasing my patents, the polyethylene from which the chlorosulfonated polyethylene is prepared should have a melt index of from about 4 to about 500. A preferred chlorosulfonated polyethylene polymer resin is prepared from branched polyethylene and has a chemical structure resembling the structure appearing immediately below ##STR3## One such preferred chlorosulfonated polyethylene polymer resin, marketed under the trademark "HYPALON 30" is currently commercially available from E. I. Du Pont de Nemours & Company of Wilmington, Del., 19898. The "HYPALON 30" brand of chlorosulfonated polyethylene polymer resin, more specifically, is known to contain about 43% by weight chlorine and about 34 millimoles of sulfonyl chloride moiety per 100 grams of polymer resin, is known to be made from branched polyethylene having a melt index of about 100, and is known to have certain other physical properties, such as those properties outlined in Table I presented below. See also, for example, the U.S. Pat. No. 4,226,954 to Pelosi, which is herein incorporated by reference.

Table I-A, also appearing below, presents other preferred varieties of chlorosulfonated polyethylene (CSPE). These varieties, sold under the "HYPALON" trademark, are currently commercially available from E. I. Du Pont de Nemours & Co. Use of these other varieties (or types) of chlorosulfonated polyethylene will be presented below in connection with example VII.

Of the preferred varieties of chlorosulfonated polyethylene presented herein, however, HYPALON 30 is the most-preferred variety thereof.

                  TABLE I                                                          ______________________________________                                         Chlorine Content, Weight %                                                                         43                                                         Sulfur Content, Weight %                                                                           1.1                                                        Specific Gravity    1.27                                                       Mooney Viscosity    30                                                         at 100 degrees C.                                                              [212 degrees F.]                                                               Brookfield Viscosity,                                                          mPa · s[cP]                                                           25 wt % in toluene  400[400]                                                   5 wt % in xylene    4[4]                                                       ______________________________________                                    

                  TABLE 1-A                                                        ______________________________________                                         "HYPALON" CSPE Type                                                                             20        LD-999   48S                                        ______________________________________                                         Chlorine content, weight %                                                                      29        35       43                                         Sulfur content, weight %                                                                        1.4       1.0      1.0                                        Specific gravity 1.12      1.18     1.26                                       Mooney viscosity at                                                                             28        30       62                                         100° C. [212° F.]                                                Brookfield viscosity,                                                          mPa-S [cP]                                                                     25 wt % in toluene                                                                              1300[1300]                                                                               --       --                                         5 wt % in xylene 9[9]      18[18]   12[12]                                     ______________________________________                                    

The composition also preferably includes a catalyst activator (or initiator). Throughout this application, the terms "activator" or "initiator" are used interchangeably and generally mean an aldehyde-amine condensation product, organic sulfonyl chlorides or mixtures thereof. For example, such a condensation product can be made from butyraldehyde and a primary amine, such an amine being, for example, aniline or butylamine.

On the other hand, certain well known catalysts (e.g. heat-activatable peroxides or azodiisobutyronitrile), when heated above room temperatures to induce their decomposition, are known to catalyze (without the preferred catalyst activators being present), thereby causing polymerization of the monomers; and inclusion (in the composition) of catalyst activators (or initiators) is therefore not crucial. However, certain well known promotors (e.g. cobalt, copper and other transition metal compounds) are often added to aid heat induced peroxide decomposition.

Furthermore, ultraviolet light and other forms of radiant energy may be used instead of heat to induce polymerization in the absence of the preferred activators. See, for example, The Chemistry of Organic Film Formers, by D. H. Solomon, published by Robert E. Krieger Publishing Co., (1977), at pages 12-14; and Plastics Polymer and Science Technology, edited by M. D. Baijal, published by John Wiley & Sons (1982) at pages 604-605.

In general, however, the present invention includes activators. Condensation products of aliphatic aldehydes with aliphatic or aromatic amines, moreover, are preferred as such activators.

In the absence of such condensation products, an organic substance having sulfonyl chloride moieties is preferred. Most preferably, however, the initiator (or activator) comprises a condensation product of butyraldehyde and aniline. One such butyraldehyde-aniline condensation product, marketed under the trademark "VANAX 808", is currently commercially available from the R. T. Vanderbilt Company, Inc., 230 Park Avenue, New York, N.Y., 10017.

Also usable as catalyst initiators, in combination with or in place of the above-described initiators, are the tertiary amines which I mention in my above-cited U.S. Pat. No. 4,112,013 (at column 2, lines 10-13) and which I herein incorporated by reference.

The chlorosulfonated polyethylene polymer resin used contained sulfonyl chloride moiety which functions as a catalyst activator (or initiator). For certain adhesive compositions presented below, which do not include chlorosulfonated polyethylene polymer resin, certain organic sulfonyl chloride derivatives, such as, for example, propane sulfonyl chloride, or para-toluene sulfonyl chloride have been added to the adhesive composition to make up for the absence of sulfonyl chloride moiety.

The adhesive composition of the present invention further also includes a graft co-polymer resin. Generally speaking, the graft co-polymer resins of the present invention comprise particles of rubber or rubber-like cores or networks which are surrounded, and may even be encapsulated, by relatively hard shells. Such graft co-polymer resins, moreover, as briefly discussed above, have generally been found useful as physical property-modifiers of PVC, or other normally-rigid plastics or the like. See, for example, U.S. Pat. No. 3,845,164 to Goto et al. Such physical property modifiers, moreover, have been found to increase flexibility and impact resistance of many normally-rigid plastics. In such a use, the graft co-polymer is generally a relatively small particle which, for example, can be dispersed throughout the normally-rigid plastic prior to injection molding thereof. Upon being thus dispersed throughout the plastic, the graft co-polymer resin particles, moreover, are generally not known to swell or otherwise react with the plastic.

In examples disclosed below, however, the preferred graft co-polymer particles have been observed to "swell" in size, and seem to react or otherwise interact with polymerizing monomeric components of the composition. Most ABS resins which are included in injection-moldable plastic compositions (for reasons outlined above), on the other hand, do not swell but rather appear to dissolve therein. As to the instant invention, however, when the preferred graft co-polymer resin particles were included in the below-presented adhesive compositions, it was observed that the preferred graft co-polymer particles generally swelled in size, became relatively gel-like and provided improved spreading and flow properties to the uncured adhesive compositions (discussed below).

Such improved flow properties are highly desirable in certain adhesive applications. For example, when an adhesive is applied to an article by means of a syringe-type applicator, many commercially available adhesives undesirably form a "string" of adhesive which generally extends from a first point on the article (where the adhesive was applied) to a second point (a subsequent position of the applicator) spaced from the first point. When the present invention was tested in just such an applicator, the flow properties of the present invention were such that a relatively small droplet of such adhesive was topically appliable to the point of application on the article to be bonded, with no adhesive string extending therefrom. Such a flow property of the present invention has also been tested for use in the field of adhesion of relatively small parts (for example, electronic parts) and the invention appears to be acceptable for such a use. During performance of the syringe-type applicator test, it was observed that certain effective, but relatively less-preferred graft co-polymer resins (e.g., ABS molding-grade resin) also appeared to dissolve in the methacrylate-based ester monomer.

In the instant invention, the methacrylate-based ester and methacrylate-based acid monomers polymerize and attach themselves to the chlorosulfonated polyethylene polymer resin particles. The mechanics of such attachment and polymerization are currently not completely known in detail. For example, it is not known to what extent attachment or polymerization occurs, nor is the order (of attachment and polymerization) known. At least some of these monomers, however, are believed to become attached during the initiation step of polymerization reaction or reactions.

The ester and acid monomers, moreover, are currently thought to penetrate the shell of individual graft co-polymer resin particles and polymerize therein thereby causing the shell or core or both to swell in size.

Regardless of theory, however, what has been observed when adhesive compositions comprising acrylate-based (preferably methacrylate-based) ester and acid monomers which have had chlorosulfonated polyethylene polymer and graft co-polymer resin particles included therewithin, is an adhesive composition having a surprising combination of enhanced overall adhesive and flow physical properties.

Preferred graft co-polymer resins are selected from the group consisting of acrylonitrile-butadiene-styrene (ABS), methacrylate-butadiene-styrene (MBS), methacrylate-acrylonitrile-butadiene-styrene (MABS), acrylate-styrene-acrylonitrile (ASA), all-acrylics, styrene-acrylonitrile grafted onto elastomeric backbones of ethylene-propylene-diene-monomer (SA EPDM), and methacrylic-acrylic rubber-styrene (MAS). More-preferred graft co-polymer resins are selected from the group consisting of MABS, ASA, all-acrylic and MBS. Most-preferred graft co-polymer resins are selected from the group consisting of MABS and ASA.

The ABS graft co-polymer resin preferably has a styrene-butadiene rubber core and a styrene-acrylonitrile shell.

The MBS graft co-polymer resin preferably has a styrene-butadiene rubber core and a shell of acrylic polymer or co-polymer.

The MABS graft co-polymer resin preferably has a styrene-butadiene rubber core and a shell of methacrylate-acrylonitrile co-polymer. More preferably, the MABS graft co-polymer resin has a core, which is approximately 75% by weight of the total weight thereof, which consists of butadiene and styrene in the weight ratio of about 50:25, and a shell of methyl methacrylate and acrylonitrile in the weight ratio of about 20:5.

The preferred ASA graft co-polymer resin is substantially as disclosed in U.S. Pat. No. 3,944,631 to Yu et al, which patent is herein incorporated by reference. That is, unlike the remainder of the above-described graft co-polymer resins, the preferred ASA graft co-polymer resin contained relatively little grafting (column 1, lines 31-32 in connection with column 8, lines 9-45 and column 9, lines 1-20). A most-preferred ASA graft co-polymer resin, marketed under the trademark "SCC 1015" (see Table II below), is substantially as described in the '631 patent and includes a crosslinked acrylate elastomer, a crosslinked styrene-acrylonitrile co-polymer and a linear styrene-acrylonitrile co-polymer. The most-preferred ASA graft co-polymer resin, moreover, appears morphologically to be made of interpenetrating polymer networks.

Preferred all-acrylic graft co-polymer resins are as disclosed in U.S. Pat. No. 3,985,703 to Ferry et al, which patent is herein incorporated by reference. Most-preferred all-acrylic graft co-polymer resins, marketed under the Trademarks "KM 323 B" and "KM 330" (see Table II below), have a rubber-type core which is approximately 75% of the total weight thereof, which consists of butyl methacrylate-type monomers and a shell of methyl methacrylate.

Examples of preferred, more-preferred and most-preferred graft co-polymer resins, discussed immediately above, which are currently commercially available and which are marketed under a variety of trademarks of well-known manufacturers, appear below in Table II.

                                      TABLE II                                     __________________________________________________________________________     TYPE OF GRAFT                                                                  CO-POLYMER                                                                     RESIN     TRADEMARK  MANUFACTURER                                              __________________________________________________________________________     ABS       ABSON 120  MOBAY CHEMICAL CO.                                                             PENN LINCOLN PARKWAY WEST                                                      PITTSBURGH, PA 15205                                                ABSON 161  MOBAY CHEMICAL CO.                                                             PENN LINCOLN PARKWAY WEST                                                      PITTSBURGH, PA 15205                                                ABSON 171  MOBAY CHEMICAL CO.                                                             PENN LINCOLN PARKWAY WEST                                                      PITTSBURGH, PA 15205                                                XP90030.01 THE DOW CHEMICAL CO.                                                           MIDLAND, MI 48640                                                   XP74027.00 THE DOW CHEMICAL CO.                                                           MIDLAND, MI 48640                                         MBS       KM 611     ROHM & HAAS CO.                                                                INDEPENDENCE MALL WEST                                                         PHILADELPHIA, PA 19105                                              KM 608A    ROHM & HAAS CO.                                                                INDEPENDENCE MALL WEST                                                         PHILADELPHIA, PA 19105                                              KM 653     ROHM & HAAS CO.                                                                INDEPENDENCE MALL WEST                                                         PHILADELPHIA, PA 19105                                              KM 641     ROHM & HAAS CO.                                                                INDEPENDENCE MALL WEST                                                         PHILADELPHIA, PA 19105                                              KM BTA-IIIS                                                                               ROHM & HAAS CO.                                                                INDEPENDENCE MALL WEST                                                         PHILADELPHIA, PA 19105                                              KM BTA-IIIF                                                                               ROHM & HAAS CO.                                                                INDEPENDENCE MALL WEST                                                         PHILADELPHIA, PA 19105                                              8003 B-X P THE DOW CHEMICAL CO.                                      MABS      ACRYLOID KM 452                                                                           ROHM & HAAS CO.                                                     BLENDEX 452                                                                               BORG-WARNER CHEMICALS, INC.                                                    TECHNICAL CENTRE                                                               WASHINGTON, WV 26181                                      ASA       SCC 1015   STAUFFER CHEMICAL CO.                                                          299 PARK AVE.                                                                  NEW YORK, NY 10017                                        ALL-      KM 323B    ROHM & HAAS CO.                                           ACRYLIC   KM 330     ROHM & HAAS CO.                                           SA EPDM   ROVEL      UNIROYAL CHEMICAL                                                              DIVISION OF UNIROYAL, INC.                                                     NAUGATUCK, CT 06770                                       MAS       VITAX      HITACHI, LTD.                                                                  TOKYO, JAPAN                                              __________________________________________________________________________

Experimental Procedure

Unless indicated otherwise, adhesive compositions were prepared by combining two separate (i.e., distinct) mixtures of methyl methacrylate ester monomer. One of the two monomer mixtures contained the chlorosulfonated polyethylene resin. The other of the monomer mixtures contained the graft co-polymer resin. The mixtures were independently (i.e., separately) mixed, preferably using a "HOBART" mixer, and thereafter blended together, preferably using a "HOCKMEYER" high-speed dispersion apparatus, to make the adhesive compositions disclosed below.

Adhesive strength (i.e., compression shear) of bonds, as between plastic materials, formed from such adhesive compositions were measured using a modification of a test outlined in ASTM D905-49. To test compression shear strength, for example, adhesive-bond test specimens consisted of a first 25 mm×25 mm×6.3 mm plastic coupon bonded to a second 25 mm×50 mm×6.3 mm plastic coupon, substantially in accordance with the ASTM D905-49 test method mentioned above. The area of each coupon to be bonded was coated with a surface activator, such as, for example, the well-known condensation product of butyraldehyde and aniline discussed above. The surface activator, currently being sold commercially under the trademark "VANAX 808", moreover, included about 0.1 weight percent of copper naphthanate which had been added thereto. Then an effective amount of adhesive composition for substantially covering the area to be bonded was applied to one of the coupons, and the two coupons were thereafter pressed together. A 0.25 mm metal shim washer was used to measure (or gauge) the bond thicknesses. After conditioning for two days at room temperature (as used herein, "room temperature" is defined to be 25 degrees Centigrade), the coupons were thereafter tested in compression shear (substantially as specified in ASTM D905-49) using a crosshead speed of 1.27 mm per minute.

Adhesive shear strength of adhesive bonds formed between cold-rolled steel coupons were tested, in accordance with the test method of ASTM D-1002-64, using like pairs of 25 mm×76 mm×1.6 mm coupons. Such coupons were first washed with methyl ethyl ketone (MEK), grit blasted, and thereafter re-washed with MEK prior to being tested. Coupon surfaces were preferably coated with the butyraldehyde-aniline condensation-product surface activator (discussed immediately above), and thereafter had the adhesive composition applied thereto, also generally as described above, except that a mold was used to index the coupons to provide uniform bonds having an area of about 12.5 mm×25 mm and a thickness of about 0.2 mm. Such bonds were conditioned for two days at room temperature, and thereafter tested at a separation rate of 1.27 mm per minute.

Peel strength of the adhesive compositions were tested according to the test method of ASTM D-1876-61T, using a pair of like 25 mm×254 mm×0.5 mm cold-rolled steel coupons. The coupons were first washed with MEK, abraded with sandpaper, and thereafter re-cleaned with MEK. Approximately 9 inches of the length of one such coupon was bonded to approximately 9 inches of the length of the other coupon, using the activation and application technique described immediately above, except that 0.18 mm wire spacers were used to measure (or gauge) bond thicknesses as the coupons were pressed together with weights in accordance with the testing method of ASTM D-1876-61T. After conditioning for two days at room temperature, the samples were tested in 180 degree peel at a rate of 254 mm per minute.

Impact strength of the adhesive compositions disclosed below were tested generally according to ASTM D950-54, except that 12.7 mm (in diameter) steel bars (or rods) having lengths of 76.2 mm and 9.5 mm respectively were used instead of test specimens having dimensions specified in the testing method of ASTM D950-54. Surfaces to be bonded together were first solvent cleaned, then grit blasted, then activated, then bonded together, and thereafter conditioned for two days at room temperature prior to testing.

For the adhesive compositions disclosed below, a cure time of from about 6 to about 8 hours resulted in achieving approximately 80% or more of ultimate bond strength.

Preferred Adhesive Compositions

Example I, presented below, discloses the performance of adhesive compositions containing varying ratios of chlorosulfonated polyethylene polymer resin to MABS graft co-polymer resin. Adhesive properties of the compositions were determined by conducting compression shear strength, lap shear strength, peel strength and impact strength tests thereon in accordance with procedures outlined above. Viscosity of adhesives nos. 1 and 2 were determined using a No. 3 spindle at 10 rpm. Viscosity of adhesives nos. 3, 4 and 5 were determined using a No. 4, a "TB" and a "TF" spindle, respectively, at 10 rpm.

EXAMPLE I

    ______________________________________                                         COMPOSITION,                                                                   PARTS BY    ADHESIVE NO.                                                        WEIGHT     1      2       3     4      5                                      ______________________________________                                         40% CSPE.sup.1                                                                             100    75      50    25     0                                      polymer resin                                                                  (HYPALON 30)                                                                   in MMA.sup.2 monomer                                                           25% MABS graft                                                                             0      25      50    75     103.sup.3                              co-polymer resin                                                               (BLENDEX 452)                                                                  in MMA.sup.2 monomer                                                           Methacrylic Acid                                                                           5      5       5     5      5                                      CHP.sup.4   0.5    0.5     0.5   0.5    0.5                                    p-toluenesulfonyl                                                                          0      0       0     0      1.26                                   chloride.sup.5                                                                 Total of CSPE.sup.1                                                                        40     36.25   32.5  28.75  35.5                                   polymer plus graft                                                             co-polymer                                                                     Ratio of CSPE.sup.1                                                                        40:0   30:6.25 20:12.5                                                                              10:18.75                                                                              0:35.5                                 polymer to graft                                                               co-polymer                                                                     Brookfield  8800   14,800  25,600                                                                               36,800 1,240,000                              Viscosity, cps                                                                 Compression                                                                    shear, psi                                                                     ABS coupons 1295   1405    1495  1070   1125                                   PVC.sup.6 coupons                                                                          1630   2175    2400  1785   1765                                   Poly-MMA.sup.2                                                                             1195   1475    2725  2045   2000                                   coupons                                                                        Lap shear, psi                                                                             3180   n.t..sup.7                                                                             4300  n.t..sup.7                                                                            1605                                   (Steel coupons)                                                                Peel strength, pli                                                                         22.5   27      29    26.5   35                                     Impact Strength,                                                                           15.7   n.t..sup.7                                                                             20.3  n.t..sup.7                                                                            22.6                                   ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 Based on 34.5% MABS graft copolymer resin in MMA monomer.               .sup.4 CHP = cumene hydroperoxide                                              .sup.5 Added to activate the cure of the adhesive in the absence of            sulfonyl chloride moiety, otherwise usually provided by the                    chlorosulfonated polyethylene polymer resin.                                   .sup.6 PVC = polyvinyl chloride                                                .sup.7 n.t. = not tested                                                 

Example IA, presented below, further discloses the performance of adhesive compositions containing varying ratios of chlorosulfonated polyethylene polymer resin to MABS graft co-polymer resin, but at a substantially constant chlorosulfonated polyethylene polymer plus graft co-polymer solids level, and thereafter again noting the adhesive properties of the compositions (relative to Example I), so as to separate out effects which might otherwise be caused by variation of such solids level. Again, the adhesive properties of the compositions were determined by conducting compression shear strength, lap shear strength, peel strength and impact strength tests thereon in accordance with procedures outlined above. Viscosity of adhesive no. 6 was determined using a No. 2 spindle at 20 rpm. Viscosity of adhesives nos. 7, 8 were determined using a "TA" spindle at 20 rpm. Viscosity of adhesives nos. 9-12 were determined using a "TC" spindle at 10 rpm.

    __________________________________________________________________________     COMPOSITION,                                                                               ADHESIVE NO.                                                       PARTS BY WEIGHT                                                                            6   7   8    9    10   11  12                                      __________________________________________________________________________     CSPE.sup.1 polymer                                                                         34.8                                                                               27.8                                                                               20.9 17.4 13.9 7.0 0                                       resin                                                                          (HYPALON 30)                                                                   MABS graft  0   7.0 13.9 17.4 20.9 27.8                                                                               34.8                                    co-polymer resin                                                               (BLENDEX 452)                                                                  MMA.sup.2 monomer                                                                          65.2                                                                               65.2                                                                               65.2 65.2 65.2 65.2                                                                               65.2                                    Methacrylic acid                                                                           5.0 5.0 5.0  5.0  5.0  5.0 5.0                                     CHP.sup.3   0.5 0.5 0.5  0.5  0.5  0.5 0.5                                     Propane sulfonyl                                                                           0   0.34                                                                               0.67 0.84 1.01 1.35                                                                               1.69                                    chloride.sup.4                                                                 Total of CSPE.sup.1                                                                        34.8                                                                               34.8                                                                               34.8 34.8 34.8 34.8                                                                               34.8                                    polymer plus graft                                                             co-polymer                                                                     Ratio of CSPE.sup.1                                                                        34.8:0                                                                             27.8:7.0                                                                           20.9:13.9                                                                           17.4:17.4                                                                           13.9:20.9                                                                           7.0:27.8                                                                           0:34.8                                  polymer to graft                                                               co-polymer                                                                     Brookfield  2240                                                                               7200                                                                               43,200                                                                              92,000                                                                              120,000                                                                             208,000                                                                            264,000                                 Viscosity,                                                                     cps                                                                            Compression shear,                                                             psi                                                                            ABS coupons 1550.sup.5                                                                         1525.sup.5                                                                         1350.sup.5                                                                          1250.sup.5                                                                          1350.sup.5                                                                          1225.sup.5                                                                         1200                                    PVC.sup.6 coupons                                                                          2200.sup.5                                                                         2000.sup.5                                                                         2000.sup.5                                                                          1900.sup.5                                                                          1850.sup.5                                                                          1900.sup.5                                                                         1525                                    Poly-MMA.sup.2                                                                             2650                                                                               2750                                                                               2650 2250 2375 1525                                                                               nil                                     coupons                                                                        Lap shear, psi                                                                             3125                                                                               4275                                                                               4225 4090 3870 3740                                                                               3180                                    steel coupons                                                                  Peel strength, pli                                                                         27.5                                                                               35  39   38   38.5 34.5                                                                               30                                      Impact strength,                                                                           17.4                                                                               22.5                                                                               23.2 24.8 20.9 21.1                                                                               18.3                                    ft-lb/sq-in                                                                    __________________________________________________________________________      Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 Added in varying amounts to activate the cure of the adhesive in        the absence of sulfonyl chloride moiety, otherwise provided by the             chlorosulfonated polyethylene polymer resin.                                   .sup.5 Coupon failed at noted value.                                           .sup.6 PVC = polyvinyl chloride                                          

Example II, presented below, discloses performance of adhesive compositions when other methacrylate-based monomers, as compared to methyl methacrylate monomer, are used in place of methyl methacrylate monomer. To various percentages of MABS graft co-polymer resin in disclosed methacrylate-based monomers were added: chlorosulfonated polyethylene polymer resin, methacrylic acid, cumene hydroperoxide, and para-toluene sulfonyl chloride, in proportions substantially the same as those of adhesive No. 3 in Example I. Also, as provided in Example I, about 40%, by weight, of chlorosulfonated polyethylene polymer resin (HYPALON 30) was included in separate mixtures as to each particular methacrylate-based monomer being tested.

EXAMPLE II

    ______________________________________                                                  Adhesive No.                                                                                         16    17                                        MA.sup.1 monomer                                                                          13      14     15   cyclo-                                                                               2-ethyl                                                                              18                                  used       methyl  ethyl  butyl                                                                               hexyl hexyl THF.sup.2                           ______________________________________                                         Percent MABS                                                                              25      25     27   24    19    25                                  graft co-polymer                                                               resin (BLENDEX                                                                 452) in MA.sup.1                                                               monomer used                                                                   Compression                                                                    shear, psi                                                                     ABS coupons                                                                               1240    1275   540  100   525   545                                 PVC.sup.3 coupons                                                                         CF.sup.4                                                                               CF.sup.4                                                                              1745 510   590   750                                 Poly-MMA.sup.5                                                                            3140    1515   1345 200   730   660                                 coupons                                                                        Lap Shear, psi                                                                            3740    3375   2560 1400  1125  3070                                Steel coupons                                                                  Peel Strength,                                                                            34      33     7-25.sup.6                                                                          1     5-15.sup.6                                                                           3                                   pli                                                                            Impact Strength                                                                           20      16     12   5     3     5                                   ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 MA = methacrylate                                                       .sup.2 THF = Tetrahydrofurfuryl                                                .sup.3 PVC = polyvinyl chloride                                                .sup.4 CF = Coupon failed                                                      .sup.5 MMA = methyl methacrylate                                               .sup.6 A sawtooth pattern was being produced on recording chart (i.e., th      bond grabs and slips).                                                   

Example III, presented below, discloses performance of adhesive compositions which included various ratios of chlorosulfonated polyethylene polymer resin to ASA graft co-polymer resin.

EXAMPLE III

    ______________________________________                                         COMPOSITION,                                                                   PARTS BY   ADHESIVE NO.                                                        WEIGHT     19      20      21     22     23                                    ______________________________________                                         40% CSPE.sup.1                                                                            100     75      50     25     0                                     polymer resin                                                                  (HYPALON 30)                                                                   in MMA.sup.2                                                                   monomer                                                                        22.5% ASA graft                                                                           0       25      50     75     100                                   co-polymer resin                                                               (SCC 1015) in                                                                  MMA.sup.2 monomer                                                              Methacrylic acid 5                                                                        5       5       5      5                                            CHP.sup.3  0.5     0.5     0.5    0.5    0.5                                   p-toluene sulfonyl                                                                        0       0       0      0      1.26.sup.4                            chloride                                                                       Total of CSPE.sup.1                                                                       40      35.63   31.25  26.88  22.5                                  polymer plus                                                                   graft co-polymer                                                               Ratio of CSPE.sup.1                                                                       40:0    30:5.63 20:11.25                                                                              10:16.88                                                                              0:22.5                                polymer to                                                                     graft co-polymer                                                               Compression                                                                    shear, psi                                                                     ABS coupons                                                                               1550    1065    1100   475    1415                                  PVC.sup.5 coupons                                                                         C.F..sup.6                                                                             C.F..sup.6                                                                             2050   1640   C.F..sup.6                            Poly-MMA.sup.2                                                                            3025    1900    1875   1850   1700                                  coupons                                                                        Lap Shear, psi                                                                            3420    4400    4290   4290   4030                                  Steel coupons                                                                  Peel Strength,                                                                            15      24      27     25     10                                    pli                                                                            Impact Strength,                                                                          16.5    n.t..sup.7                                                                             15     n.t.sup.7                                                                             14                                    ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 Added to activate the cure of the adhesive in the absence of            sulfonyl chloride moiety, otherwise usually provided by the                    chlorosulfonated polyethylene polymer resin                                    .sup.5 PVC = polyvinyl chloride                                                .sup.6 C.F. = Coupon failed                                                    .sup.7 n.t. = not tested                                                 

Examples III-A and III-B, presented below, disclose performance of adhesive compositions, which include varying ratios of chlorosulfonated polyethylene polymer resin to all-acrylic graft co-polymer resins.

EXAMPLE III-A

    ______________________________________                                         COMPOSITION      ADHESIVE NO.                                                  PARTS BY WEIGHT  24       25       26                                          ______________________________________                                         40% CSPE.sup.1   75       50       25                                          polymer resin                                                                  (HYPALON 30) in                                                                MMA.sup.2 monomer                                                              17.5% All Acrylic                                                                               25       50       75                                          graft co-polymer                                                               resin (KM 323 B)                                                               in MMA.sup.2 monomer                                                           Methacrylic acid 5        5        5                                           CHP.sup.3        0.5      0.5      0.5                                         Total of CSPE.sup.1                                                                             34.38    28.75    23.13                                       polymer plus graft                                                             co-polymer                                                                     Ratio of CSPE.sup.1                                                                             30:4.38  20:8.75  10:13.13                                    polymer to graft                                                               co-polymer                                                                     Compression shear, psi                                                         ABS coupons      1300     1325     875                                         PVC.sup.4 coupons                                                                               2000     1725     1200                                        Poly-MMA.sup.2   2175     3450     2525                                        coupons                                                                        Lap Shear (steel 4110     4200     3610                                        coupons), psi                                                                  Peel strength, pli                                                                              30       18       13                                          Impact strength, 12.7     10.6     9.2                                         ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 PVC = polyvinyl chloride                                          

EXAMPLE III-B

    ______________________________________                                         COMPOSITION,     ADHESIVE NO.                                                  PARTS BY WEIGHT  27       28       29                                          ______________________________________                                         40% CSPE.sup.1   75       50       25                                          polymer resin                                                                  (HYPALON 30) in                                                                MMA.sup.2 monomer                                                              18.1% All Acrylic                                                                               25       50       75                                          graft co-polymer                                                               resin (KM 330) in                                                              MMA.sup.2 monomer                                                              Methacrylic Acid 5        5        5                                           CHP.sup.3        0.5      0.5      0.5                                         Total of CSPE.sup.1                                                                             34.53    29.05    23.58                                       polymer plus                                                                   graft co-polymer                                                               Ratio of CSPE.sup.1                                                                             30:4.53  20:9.05  10:13.58                                    polymer to                                                                     graft co-polymer                                                               Compression shear, psi                                                         ABS coupons      825      1050     675                                         PVC.sup.4 coupons                                                                               C.F..sup.5                                                                              C.F..sup.5                                                                              1350                                        Poly-MMA.sup.2   1890     2115     1390                                        coupons                                                                        Lap shear (steel 4175     4090     3730                                        coupons), psi                                                                  Peel strength, pli                                                                              31       32       33                                          Impact strength, n.t..sup.6                                                                              n.t..sup.6                                                                              n.t..sup.6                                  ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 PVC = polyvinyl chloride                                                .sup.5 C.F. = Coupon failed                                                    .sup.6 n.t. = nottested                                                  

Examples III-C through III-G, presented below, disclose performance of adhesive compositions, which include varying ratios of chlorosulfonated polyethylene polymer resin to MBS graft co-polymer resins. As between these MBS graft co-polymer resins, the KM 641 (Example III-E) has a relatively smaller particle size than the KM 611 (Example III-D), which in turn has a relatively smaller particle size than the KM 653 (Example III-F).

EXAMPLE III-C

    ______________________________________                                         COMPOSITION     ADHESIVE NO.                                                   PARTS BY WEIGHT 30       31        32                                          ______________________________________                                         40% CSPE.sup.1  75       50        25                                          polymer resin                                                                  (HYPALON 30) in MMA.sup.2                                                      monomer                                                                        32.25% MBS graft                                                                               25       50        75                                          co-polymer resin                                                               (KM 608A) in MMA.sup.2                                                         Methacrylic acid                                                                               5        5         5                                           CHP.sup.3       0.5      0.5       0.5                                         Total of CSPE.sup.1                                                                            38.13    36.25     34.38                                       polymer plus                                                                   graft co-polymer                                                               Ratio of CSPE.sup.1                                                                            30:8.13  20:16.25  10:24.38                                    polymer to                                                                     graft co-polymer                                                               Compression shear, psi                                                         ABS coupons     n.t..sup.4                                                                              300       n.t..sup.4                                  PVC.sup.5 coupons                                                                              n.t..sup.4                                                                              1250      n.t..sup.4                                  Poly MMA.sup.2  n.t..sup.4                                                                              1200      n.t..sup.4                                  coupons                                                                        Lap shear (steel                                                                               4065     3980      1190                                        coupons), psi                                                                  Peel strength, pli                                                                             n.t..sup.4                                                                              26        n.t..sup.4                                  Impact strength,                                                                               n.t..sup.4                                                                              15        n.t..sup.4                                  ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 n.t. = not tested                                                       .sup.5 PVC = polyvinyl chloride                                          

EXAMPLE III-D

    ______________________________________                                         COMPOSITION     ADHESIVE NO.                                                   PARTS BY WEIGHT 33       34        35                                          ______________________________________                                         40% CSPE.sup.1  75       50        25                                          polymer resin                                                                  (HYPALON 30) in MMA.sup.2                                                      monomer                                                                        31.8% MBS graft 25       50        75                                          co-polymer resin                                                               (KM 611) in MMA.sup.2                                                          monomer                                                                        Methacrylic acid                                                                               5        5         5                                           CHP.sup.3       0.5      0.5       0.5                                         Total of CSPE.sup.1                                                                            37.95    35.90     33.85                                       polymer plus                                                                   graft co-polymer                                                               Ratio of CSPE.sup.1                                                                            30:7.95  20:15.90  10:23.85                                    polymer to                                                                     graft co-polymer                                                               Compression shear, psi                                                         ABS coupons     n.t..sup.4                                                                              775       n.t..sup.4                                  PVC.sup.5 coupons                                                                              n.t..sup.4                                                                              1025      n.t..sup.4                                  Poly-MMA.sup.2  n.t..sup.4                                                                              2200      n.t..sup.4                                  coupons                                                                        Lap Shear (steel                                                                               4310     4125      3550                                        coupons), psi                                                                  Peel strength, pli                                                                             n.t..sup.4                                                                              30        n.t..sup.4                                  Impact strength,                                                                               n.t..sup.4                                                                              19.4      n.t..sup.4                                  ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 n.t. = not tested                                                       .sup.5 PVC = polyvinyl chloride                                          

EXAMPLE III-E

    ______________________________________                                         COMPOSITION     ADHESIVE NO.                                                   PARTS BY WEIGHT 36       37        38                                          ______________________________________                                         40% CSPE.sup.1  75       50        25                                          polymer resin                                                                  (HYPALON 30) in MMA.sup.2                                                      monomer                                                                        35% MBS graft   25       50        75                                          co-polymer resin                                                               (KM 641) in MMA.sup.2                                                          monomer                                                                        Methacrylic acid                                                                               5        5         5                                           CHP.sup.3       0.5      0.5       0.5                                         Total of CSPE.sup.1                                                                            38.75    37.50     36.25                                       polymer plus                                                                   graft co-polymer                                                               Ratio of CSPE.sup.1                                                                            30:8.75  20:17.50  10:26.25                                    polymer to                                                                     graft co-polymer                                                               Compression shear, psi                                                         ABS coupons     n.t..sup.4                                                                              350       n.t..sup.4                                  PVC.sup.5 coupons                                                                              n.t..sup.4                                                                              1075      n.t..sup.4                                  Poly-MMA.sup.2  n.t..sup.4                                                                              1375      n.t..sup.4                                  coupons                                                                        Lap shear (steel                                                                               4220     3660      2660                                        coupons), psi                                                                  Peel strength, pli                                                                             n.t..sup.4                                                                              15        n.t..sup.4                                  Impact strength,                                                                               n.t..sup.4                                                                              12.3      n.t..sup.4                                  ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 n.t. = not tested                                                       5 PVC = polyvinyl chloride                                               

EXAMPLE III-F

    ______________________________________                                         COMPOSITION,    ADHESIVE NO.                                                   PARTS BY WEIGHT 39       40        41                                          ______________________________________                                         40% CSPE.sup.1  75       50        25                                          polymer resin                                                                  (HYPALON 30) in MMA.sup.2                                                      monomer                                                                        24.1% MBS graft 25       50        75                                          co-polymer resin                                                               (KM 653) in MMA.sup.2                                                          monomer                                                                        Methacrylic acid                                                                               5        5         5                                           CHP.sup.3       0.5      0.5       0.5                                         Total of CSPE.sup.1                                                                            36.03    32.05     28.08                                       polymer plus                                                                   graft co-polymer                                                               Ratio of CSPE.sup.1                                                                            30:6.03  20:12.05  10:18.08                                    polymer to                                                                     graft co-polymer                                                               Compression shear, psi                                                         ABS coupons     975      365       415                                         PVC.sup.4 coupons                                                                              c.f..sup.5                                                                              1300      1025                                        Poly-MMA.sup.2  1265     1025      2475                                        coupons                                                                        Lap shear strength steel                                                                       4205     3520      nil                                         coupons, psi                                                                   Peel strength, pli                                                                             38       15        nil                                         Impact strength,                                                                               n.t..sup.6                                                                              n.t..sup.6                                                                               n.t..sup.6                                  ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 PVC = polyvinyl chloride                                                .sup.5 c.f. = coupon failed                                                    .sup.6 n.t. = not tested                                                 

EXAMPLE III-G

    ______________________________________                                         COMPOSITION,     ADHESIVE NO.                                                  PARTS BY WEIGHT  42       43       44                                          ______________________________________                                         40% CSPE.sup.1   75       50       25                                          polymer resin                                                                  (HYPALON 30) in MMA.sup.2                                                      monomer                                                                        19.6% MBS graft  25       50       75                                          co-polymer resin                                                               (8003 B-X P)                                                                   in MMA.sup.2                                                                   monomer                                                                        Methacrylic acid 5        5        5                                           CHP.sup.3        0.5      0.5      0.5                                         Total of CSPE.sup.1                                                                             34.90    29.80    24.70                                       polymer plus                                                                   graft co-polymer                                                               Ratio of CSPE.sup.1                                                                             30:4.90  20:9.80  10:14.70                                    polymer to                                                                     graft co-polymer                                                               Compression shear, psi                                                         ABS coupons      650      325      215                                         PVC.sup.4 coupons                                                                               c.f..sup.5                                                                              1325     1050                                        Poly-MMA.sup.2   1215     940      1225                                        coupons                                                                        Lap shear strength                                                                              4215     3615     3425                                        steel coupons, psi                                                             Peel strength, pli                                                                              38       41       36.5                                        Impact strength, n.t..sup.6                                                                              n.t..sup.6                                                                              n.t..sup.6                                  ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 PVC = polyvinyl chloride                                                .sup.5 c.f. = coupon failed                                                    .sup.6 n.t. = not tested                                                 

Examples IV-A through IV-E, presented below, disclose performance of adhesive compositions which include either a chlorosulfonated polyethylene polymer resin or a graft co-polymer resin, but not both. The adhesive composition of Example IV-A includes chlorosulfonated polyethylene polymer resin. The adhesive compositions of Examples IV-B through IV-D include MBS graft co-polymer resins. The adhesive composition of Example IV-E includes an all-acrylic graft co-polymer resin.

EXAMPLE IV-A

    ______________________________________                                         COMPOSITION       ADHESIVE                                                     PARTS BY WEIGHT   NO. 45                                                       ______________________________________                                         CSPE.sup.1 polymer                                                                                40                                                          resin (HYPALON 30)                                                             MMA.sup.2 monomer  60                                                          Methacrylic acid    5                                                          CHP.sup.3          0.5                                                         Compression shear, psi                                                         ABS coupons       1450                                                         PVC.sup.4 coupons c.f..sup.5                                                   Poly-MMA.sup.2    1900                                                         coupons                                                                        Lap shear, psi    3360                                                         Peel strength, pli                                                                                19                                                          Impact strength   13.5                                                         ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 PVC = polyvinyl chloride                                                .sup.5 c.f. = coupon failed                                              

EXAMPLE IV-B

    ______________________________________                                         COMPOSITION,      ADHESIVE                                                     PARTS BY WEIGHT   NO. 46                                                       ______________________________________                                         MBS graft         33.5                                                         co-polymer resin                                                               (KM 653)                                                                       MMA.sup.1 monomer 66.5                                                         Methacrylic acid   5                                                           CHP.sup.2          0.5                                                         p-toluene sulfonyl                                                                                5                                                           chloride.sup.3                                                                 Compression shear, psi                                                         ABS coupons       695                                                          PVC.sup.4 coupons 1280                                                         Poly-MMA.sup.1    595                                                          coupons                                                                        Lap shear, psi     90                                                          Peel strength, pli                                                                                1                                                           Impact strength,   1.0                                                         ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 MMA = methyl methacrylate                                               .sup.2 CHP = cumene hydroperoxide                                              .sup.3 Added to activate the cure of the adhesive in the absence of the        sulfonyl chloride moiety usually otherwise provided by the                     chlorosulfonated polyethylene polymer resin.                                   .sup.4 PVC = polyvinyl chloride                                          

EXAMPLE IV-C

    ______________________________________                                         COMPOSITION,      ADHESIVE                                                     PARTS BY WEIGHT   NO. 47                                                       ______________________________________                                         MBS graft         33.5                                                         co-polymer resin                                                               (KM 611)                                                                       MMA.sup.1 monomer 66.5                                                         Methacrylic acid   5                                                           CHP.sup.2          0.5                                                         p-toluene          5                                                           sulfonyl chloride.sup.3                                                        Compression shear, psi                                                         ABS coupons       620                                                          PVC.sup.4 coupons 525                                                          Poly-MMA.sup.1    635                                                          coupons                                                                        Lap shear, psi     35                                                          Peel strength, pli                                                                                2                                                           Impact strength,   1.3                                                         ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 MMA = methyl methacrylate                                               .sup.2 CHP = cumene hydroperoxide                                              .sup.3 Added to activate the cure of the adhesive in the absence of the        sulfonyl chloride moiety usually otherwise provided by the                     chlorosulfonated polyethylene polymer resin.                                   .sup.4 PVC = polyvinyl chloride                                          

EXAMPLE IV-D

    ______________________________________                                         COMPOSITION       ADHESIVE                                                     PARTS BY WEIGHT   NO. 48                                                       ______________________________________                                         MBS graft         33.5                                                         co-polymer resin                                                               (8003 B-X P)                                                                   MMA.sup.1 monomer 66.5                                                         Methacrylic acid   5                                                           CHP.sup.2          0.5                                                         p-toluene sulfonyl                                                                                5                                                           chloride.sup.3                                                                 Compression shear, psi                                                         ABS coupons       375                                                          PVC.sup.4 coupons 810                                                          Poly-MMA.sup.1    725                                                          coupons                                                                        Lap shear, psi    580                                                          Peel strength, pli                                                                                7                                                           Impact strength,   0.9                                                         ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 MMA = methyl methacrylate                                               .sup.2 CHP = cumene hydroperoxide                                              .sup.3 Added to activate the cure of the adhesive in the absence of the        sulfonyl chloride moiety usually otherwise provided by the                     chlorosulfonated polyethylene polymer resin.                                   .sup.4 PVC = polyvinyl chloride                                          

EXAMPLE IV-E

    ______________________________________                                         COMPOSITION,      ADHESIVE                                                     PARTS BY WEIGHT   NO. 49                                                       ______________________________________                                         All-acrylic graft 21.5                                                         co-polymer resin                                                               (KM 323 B)                                                                     MMA.sup.1         78.5                                                         Methacrylic acid   5                                                           CHP.sup.2          0.5                                                         p-toluene sulfonyl                                                                                5                                                           chloride.sup.3                                                                 Compression shear, psi                                                         ABS coupons       690                                                          PVC.sup.4 coupons 995                                                          Poly-MMA.sup.1    375                                                          coupons                                                                        Lap shear, psi    160                                                          Peel strength, pli                                                                                1                                                           Impact strength,   3.0                                                         ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 MMA = methyl methacrylate                                               .sup.2 CHP = cumene hydroperoxide                                              .sup.3 Added to activate the cure of the adhesive in the absence of the        sulfonyl chloride moiety usually otherwise provided by the                     chlorosulfonated polyethylene polymer resin.                                   .sup.4 PVC = polyvinyl chloride                                          

For the adhesive compositions of the instant invention, polymerization of the acrylate-based (preferably methacrylate-based) ester and acid monomers thereof causes the composition to set up, harden, and cure. The catalyst "triggers" the polymerization steps. The activator (or initiator) when included, in turn, triggers the catalyzation step.

In a first preferred method of practicing the present invention, the adhesive composition, excluding the activator (or initiator), is applied to at least a first one of at least two surfaces which are to be bonded together. The activator is applied to the other surface The two surfaces are then brought into such close proximity that the activator contacts the adhesive composition, whereby the activator triggers catalytic action of the catalyst. Such action by the catalyst, in turn, initiates polymerization of the monomers, whereby the composition is caused to set up, harden and cure. Such an application or method of use is generally referred to as a one-part adhesive because only a relatively small amount of activator (relative to the amount of total adhesive composition) is needed to trigger the action of the catalyst.

A second preferred method of practicing the present invention is via the combination or mixture of both parts of a so-called two-part adhesive. The two-part adhesive comprises first and second portions of the adhesive composition. The first portion includes some of the adhesive composition ingredients and the catalyst. The second portion includes the remainder of the adhesive composition components and the activator. Volumetric mix ratios of the two portions generally can range from about 5:95 to about 95:5, and 1:1 is often preferred. Regardless of the volumetric mix ratio chosen, however, the relative proportions of the catalyst and activator (or initiator) components must be selected so that effective polymerization results.

Example V, presented below, is approximately a 1:1 equal volume mixture of parts A and B. Upon parts A and B being mixed together, the adhesive composition had a working time (i e., that amount of time wherein the composition is generally acknowledged to be substantially workable or fluid-like) which lasted for up to about 2 minutes after contacting the catalyst-included portion with the initiator-included portion. More specifically, the adhesive composition began to thicken or gel in about 2.5 minutes (after having been mixed), exhibited a definite exotherm during mixing and hardening, and hardened in about 5 minutes (after initial mixing). Approximately 5 grams of part A were mixed with approximately 5 grams of part B. Larger quantities are expected to harden in less time, and exhibit a relatively more pronounced exotherm. About 80% or more of the ultimate bond strength is achieved in from about 6 to about 8 hours.

EXAMPLE V

    ______________________________________                                         COMPOSITION,      ADHESIVE                                                     PARTS BY WEIGHT   NO. 50                                                       ______________________________________                                         Part A                                                                         CSPE.sup.1 polymer                                                                               35.5                                                         resin                                                                          (HYPALON 30)                                                                   MMA.sup.2         53.2                                                         Methacrylic Acid  9.8                                                          CHP.sup.3         1.0                                                          Ionol.sup.4       0.5                                                          TOTAL, Part A     100.0                                                        Part B                                                                         MABS graft        25.0                                                         co-polymer resin                                                               (Acryloid KM 452)                                                              MMA.sup.2         75.0                                                         Initiator No. 1   4.995                                                        (VANAX 808)                                                                    Initiator No. 2   0.005                                                        (Copper Naphthanate                                                            solution).sup.5                                                                TOTAL, Part B     105.00                                                       Compression shear, psi                                                         ABS coupons       1510                                                         PVC.sup.6 coupons 2610                                                         Poly-MMA.sup.2    4200                                                         coupons                                                                        Lap Shear, psi                                                                 Grit-blasted steel                                                                               3960                                                         coupons                                                                        Peel Strength, pli                                                                               --                                                           Impact Strength,  22.6                                                         (ft-lb/sq-in)                                                                  ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide (the catalyst)                               .sup.4 Ionol is a stabilizer which serves to avoid premature gelation of       the graft copolymer resin.                                                     .sup.5 Sold commercially by Tenneco Chemicals, Inc., Heyden Division, 280      Park Avenue, New York, NY, 10017, under the NUODEX trademark.                  .sup.6 PVC = polyvinyl chloride                                          

Table III, presented below, provides additional information as to physical properties of one of the most-preferred graft co-polymer resins.

                                      TABLE III                                    __________________________________________________________________________                                   MABS GRAFT                                       PHYSICAL                                                                               TEST   ASTM           CO-POLYMER RESIN                                 PROPERTIES                                                                             METHOD CONDITION                                                                              UNITS  (BLENDEX 452)                                    __________________________________________________________________________     Tensile D-638-71                                                                              73° F.                                                                          PSI    800                                              strength                                                                               0.2 in/min                                                             Tensile D-638-71                                                                              73° F.                                                                          PSI × 10.sup.5                                                                  0.4                                              Modulus                                                                        Heat    D-648-72                                                                              264 PSI °F. @ 10 mils                                                                  118                                              Deflection             Deflection                                              (Annealed)                                                                     Specific                                                                               D-792-66,                                                                             73° F.                                                                          --     1.01                                             Gravity Method A-1                                                             Hardness D                                                                             D-530, 73° F.                                                                          --     60                                                       Type "D",                                                                      Method "A"                                                             Izod Impact,                                                                           D-256-72,                                                                             73° F.                                                                          ft-lb/in                                                                              5.5                                              1/4 in  Method "A"                                                             Bulk    --     73° F.                                                                          lb/cu-ft                                                                              16                                               Density                                                                        __________________________________________________________________________

Example VI, presented below, discloses adhesive compositions produced by varying the relative amount of methacrylic acid in the adhesive composition mixture. Relative amounts of the remainder components were held substantially constant so as to determine the effect or variation of the methacrylic acid.

Example VII, also presented below, discloses adhesive compositions containing three different varieties (or types) of chlorosulfonated polyethylene (which were discussed and presented above in connection with Table I-A) in combination with MABS graft co-polymer resin.

EXAMPLE VI

    ______________________________________                                         COMPOSITION      ADHESIVE NO.                                                  PARTS BY WEIGHT  51     52       53   54                                       ______________________________________                                         CSPE polymer      20     20       20   20                                      resin                                                                          (HYPALON 30)                                                                   MABS graft       12.5   12.5     12.5 12.5                                     co-polymer resin                                                               (BLENDEX 452)                                                                  MMA              67.5   67.5     67.5 67.5                                     Methacrylic       15     10        5    0                                      acid                                                                           CHP              0.5    0.5      0.5  0.5                                      Ionol            0.25   0.25     0.25 0.25                                     Lap shear, psi   4650   4550     4450 2300                                     ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 Ionol is a stabilizer which serves to avoid premature gelation of       the graft copolymer resin.                                                     .sup.5 Gritblasted steel coupons                                         

EXAMPLE VII

    ______________________________________                                         COMPOSITION       ADHESIVE NO.                                                 PARTS BY WEIGHT   55       56     57                                           ______________________________________                                         40% CSPE.sup.1 polymer                                                                            50      --     --                                           resin (HYPALON 20)                                                             in MMA.sup.2 monomer                                                           40% CSPE.sup.1 polymer                                                                           --        50    --                                           resin (HYPALON LD-999)                                                         in MMA.sup.2 monomer                                                           40% CSPE.sup.1 polymer                                                                           --       --     50                                           resin (HYPALON 485)                                                            in MMA.sup.2 monomer                                                           25% MABS graft     50       50    50                                           co-polymer resin                                                               (BLENDEX 452) in                                                               MMA.sup.2 monomer                                                              Methacrylic acid    5        5      5                                          CHP.sup.3          0.5      0.5    0.5                                         Compression shear, psi                                                         ABS coupons       1275     1150   n.t..sup.5                                   PVC.sup.4 coupons 1400     1450   n.t..sup.5                                   Poly-MMA.sup.2    3225     2950   n.t..sup.5                                   coupons                                                                        Lap shear, psi    3705     3705   4095                                         Peel strength, pli                                                                                33       30    33                                           Impact strength,  20.5     21.3   22.9                                         ft-lb/sq-in                                                                    ______________________________________                                          Footnotes:                                                                     .sup.1 CSPE = chlorosulfonated polyethylene                                    .sup.2 MMA = methyl methacrylate                                               .sup.3 CHP = cumene hydroperoxide                                              .sup.4 PVC = polyvinyl chloride                                                .sup.5 n.t. = not tested                                                 

What has been described herein are novel methacrylate-based compositions. While the novel methacrylate-based compositions of the invention have been described with reference to use as adhesives, the invention is not limited thereto. On the contrary, alternatives, changes or modifications may become apparent to those skilled in the art upon reading the foregoing description. Accordingly, such alternatives, changes and modifications are to be considered as forming a part of the invention insofar as they fall within the spirit and scope of the appended claims.

For example, in addition to having usefulness in the area of adhesives, it is contemplated that the present invention is generally useful in the areas of repair products, casting materials and coatings. In the repair-products field, for example, a piece of fiberglass cloth can be wetted on both sides with the present invention to make a fiberglass patch. It is further contemplated that the present invention can include an effective amount of metal particles for producing repair products having a variety of commercially desirable features.

Furthermore, in the casting-materials area, the present invention can be used as a carrier of preselected components much the way epoxies are currently used.

In the coatings field, for example, the present invention can be used to permanently coat metal substrates for a variety of reasons. 

I claim:
 1. An adhesive composition consisting of: an ester monomer wherein said monomer is an acrylate ester monomer or a methacrylate ester monomer; a catalyst; and respective effective amounts of a mixture of (1) chlorinated polyethylene polymer resin and sulfonyl chloride or (2) chlorosulfonated polyethylene polymer resin and (3) a graft co-polymer resin for providing said composition with enhanced overall adhesive physical properties, said graft co-polymer resin having a backbone polymer with a glass transition temperature substantially below ambient temeprature and a grafted polymer resin having a glass transition temperature substantially above ambient temperature, with ambient being defined as the environment range within which the adhesive is being used.
 2. The adhesive composition of claim 1 further including a catalyst activator.
 3. The adhesive composition of claim 1 further including an acrylate-based or a methacrylate-based acid monomer.
 4. An adhesive composition consisting of an ester monomer wherein said monomer is an acrylate ester monomer or a methacrylate ester monomer; an acid monomer wherein said acid monomer is an acrylic acid monomer, a methacrylic acid monomer, or a derivative of either thereof; a catalyst; a catalyst activator; and respective effective amount of a mixture of (1) chlorinated polyethylene or (2) chlorosulfonated polyethylene polymer resin and sulfonyl chloride and (3) a graft co-polymer resin for providing said composition with enhanced overall adhesive physical properties, said graft co-polymer resin having a backbone polymer with a glass transition temperature substantially below ambient temperature and a grafted polymer resin having a glass transistion temperature substantially above ambient temperature, with ambient being defined as the environment range within which the adhesive is being used.
 5. The adhesive composition of claim 4 wherein said ester monomer is methacrylate-based and is selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and tetrahydrofurfuryl methacrylate.
 6. The adhesive composition of claim 4 wherein said ester monomer is methacrylate-based and is selected from the group consisting of methyl methacrylate and ethyl methacrylate.
 7. The adhesive composition of claim 4 wherein said ester monomer is methyl methacrylate.
 8. The adhesive composition of claim 4 wherein said acid monomer is methacrylic acid.
 9. The adhesive composition of claim 4 wherein said catalyst activator is an aldehyde-amine condensation product.
 10. The adhesive composition of claim 4 wherein said catalyst activator is selected from the group consisting of aldehyde-amine condensation products, propane sulfonyl chloride and para-toluene sulfonyl chloride.
 11. The adhesive composition of claim 4 wherein said catalyst is a free-radical generator selected from the group consisting of organic peroxide, organic hydroperoxide, perester and peracid.
 12. The adhesive composition of claim 4 wherein said catalyst is cumene hydroperoxide.
 13. The adhesive composition of claim 4 wherein said chlorosulfonated polyethylene polymer resin contains about 43 weight percent chlorine, about 1.1 weight percent sulfur, and about 34 millimoles of sulfonyl chloride moiety per 100 grams thereof.
 14. The adhesive composition of claim 4 wherein said co-polymer resin is selected from the group consisting of ABS, MBS, MABS, ASA, all-acrylic, SA EPDM and MAS.
 15. The adhesive composition of claim 4 wherein said co-polymer resin is selected from the group consisting of MABS, ASA, all-acrylic and MBS.
 16. The adhesive composition of claim 4 wherein said co-polymer resin is selected from the group consisting of MABS and ASA.
 17. The adhesive composition of claim 4 wherein said enhanced adhesive physical properties include compression shear strength, lap shear strength, peel strength and impact strength.
 18. An adhesive composition consisting of: a methacrylate-based ester monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate and tetrahydrofurfuryl methacrylate; a methacrylic acid monomer; a catalyst activator selected from the goup consisting of aldehyde-amine condensation products, propane sulfonyl chloride and para-toluene sulfonyl chloride; a free-radical generating catalyst selected from the group consisting of organic peroxide, organic hydroperoxide, perester and peracid; and respective effective amounts of a mixture of (1) a chlorinated polyethylene polymer resin and sulfonyl chloride or (2) chlorosulfonated polyethylene polymer resin and (3) a graft co-polymer resin selected from the group consisting of ABS, MBS, MABS, ASA, all-acrylic, SA EPDDM and MAS for providing said composition with enhanced overall compression shear strength, lap shear strength, peel strength and impact strength, said graft co-polymer resin having a backbone polymer with a glass transistion temperature substantially below ambient temperature and a grafted polymer resin having a glass transition temperature substantially above ambient temperature, with ambient being defined as the environment range within which the adhesive is being used.
 19. The adhesive composition of claim 18 wherein said methacrylate-based ester monomer is selected from the group consisting of methyl methacrylate and ethyl methacrylate.
 20. The adhesive composition of claim 18 wherein said methacrylate-based ester monomer is methyl methacrylate monomer.
 21. The adhesive composition of claim 20 wherein said catalyst is cumene hydroperoxide.
 22. The adhesive composition of claim 21 wherein said co-polymer resin is selected from the group consisting of MABS, ASA, all-acrylic and MBS.
 23. The adhesive composition of claim 21 wherein said co-polymer resin is selected from the group consisting of MABS and ASA.
 24. The adhesive composition of claim 22 wherein said chlorosulfonated polyethylene polymer resin contains about 43 weight percent chlorine, about 1.1 weight percent sulfur and about 34 millimoles sulfonyl chloride moiety per 100 grams thereof. 